Atomic Structure
and Periodicity
The Puzzle of the Atom
 Protons and electrons are attracted to each
other because of opposite charges
 Electrically charged particles moving in a
curved path give off energy
 Despite these facts, atoms don’t collapse
Wave-Particle Duality
JJ Thomson won the Nobel prize for describing the
electron as a particle.
His son, George Thomson won the Nobel prize for
describing the wave-like nature of the electron.
The
electron is
a particle!
The
electron is
an energy
wave!
Confused??? You’ve Got Company!
“No familiar conceptions can be
woven around the electron;
something unknown is doing we
don’t know what.”
Physicist Sir Arthur Eddington
The Nature of the Physical World
1934
The Wave-like Electron
The electron propagates
through space as an energy
wave. To understand the
atom, one must understand
the behavior of
electromagnetic waves.
Louis deBroglie
Electromagnetic radiation propagates through space
as a wave moving at the speed of light.
c = λν
C = speed of light, a constant (3.00 x 108 m/s)
Υ = frequency, in units of hertz (hz, sec-1)
λ = wavelength, in meters
Types of electromagnetic radiation:
The energy (E ) of electromagnetic radiation is
directly proportional to the frequency (ν) of the
radiation.
E = hν
E = Energy, in units of Joules (kg·m2/s2)
h = Planck’s constant (6.626 x 10-34 J·s)
ν= frequency, in units of hertz (hz, sec-1)
Long
Wavelength
=
Low Frequency
=
Low ENERGY
Short
Wavelength
=
High Frequency
=
High ENERGY
Wavelength Table
Relating Frequency, Wavelength and
Energy
c 
E  h
Common re-arrangements:
E
hc

hc

E
Spectroscopic analysis of the visible spectrum…
…produces all of the colors in a continuous spectrum
Spectroscopic analysis of the hydrogen spectrum…
…produces a “bright line” spectrum
Electron transitions
involve jumps of
definite amounts of
energy.
This produces bands
of light with definite
wavelengths.
Electron Energy in Hydrogen
E electron   2.178 x10
18
Z 
J  2 
n 
2
Z = nuclear charge (atomic number)
n = energy level
***Equation works only for atoms or ions
with 1 electron (H, He+, Li2+, etc).
Calculating Energy Change, ΔE, for
Electron Transitions
2
2

Z
Z
18 
E   2.178 x 10 J 2  2
n
n
final
initial





Energy must be absorbed from a photon
(+E) to move an electron away from the
nucleus
Energy (a photon) must be given off (-E)
when an electron moves toward the nucleus
Quantum Numbers
Each electron in an atom has a unique
set of 4 quantum numbers which describe
it.
 Principal quantum number
 Angular momentum quantum number
 Magnetic quantum number
 Spin quantum number
Pauli Exclusion Principle
No two electrons in an atom
can have the same four
quantum numbers.
Wolfgang
Pauli
Principal Quantum Number
Generally symbolized by n, it denotes the shell
(energy level) in which the electron is located.
Number of electrons
that can fit in a shell:
2n2
Angular Momentum Quantum Number
The angular momentum quantum number, generally
symbolized by l, denotes the orbital (subshell) in
which the electron is located.
Magnetic Quantum Number
The magnetic quantum number, generally
symbolized by m, denotes the orientation of the
electron’s orbital with respect to the three axes in
space.
Assigning the Numbers
 The three quantum numbers (n, l, and m) are
integers.
 The principal quantum number (n) cannot be
zero.
 n must be 1, 2, 3, etc.
 The angular momentum quantum number (l )
can be any integer between 0 and n - 1.
 For n = 3, l can be either 0, 1, or 2.
 The magnetic quantum number (ml) can be any
integer between -l and +l.
 For l = 2, m can be either -2, -1, 0, +1, +2.
Principle, angular momentum, and magnetic
quantum numbers: n, l, and ml
Spin Quantum Number
Spin quantum number denotes the behavior
(direction of spin) of an electron within a
magnetic field.
Possibilities for electron spin:
1

2
1

2
An orbital is a region within an atom where there
is a probability of finding an electron. This is a probability
diagram for the s orbital in the first energy level…
Orbital shapes are defined as the surface that
contains 90% of the total electron probability.
Schrodinger Wave Equation

d

V 
8  m dx
h
2
2
2
2
 E
Equation for probability of a
single electron being found
along a single axis (x-axis)
Erwin Schrodinger
animationani
mation
Heisenberg Uncertainty Principle
“One cannot simultaneously
determine both the position
and momentum of an electron.”
You can find out where the
electron is, but not where it
is going.
Werner
Heisenberg
OR…
You can find out where the
electron is going, but not
where it is!
Sizes of s orbitals
Orbitals of the same shape (s, for instance) grow
larger as n increases…
Nodes are regions of low probability within an
orbital.
Orbitals in outer energy levels DO penetrate into
lower energy levels. Penetration #1
This is a probability
Distribution for a
3s orbital.
What parts of the
diagram correspond
to “nodes” – regions
of zero probability?
Which of the orbital types in the 3rd energy level
Does not seem to have a “node”?
WHY NOT?
Penetration #2
The s orbital has a spherical shape centered around
the origin of the three axes in space.
s orbital shape
P orbital shape
There are three dumbbell-shaped p orbitals in
each energy level above n = 1, each assigned to
its own axis (x, y and z) in space.
Things get a bit more
complicated with the five d
d orbital shapes
orbitals that are found in
the d sublevels beginning
with n = 3. To remember
the shapes, think of:
“double dumbells”
…and a “dumbell
with a donut”!
Shape of f orbitals
Orbital filling table
Electron configuration of the elements of the
first three series
Element
Lithium
Configuration
notation
Orbital notation
1s22s1
[He]2s1
____
1s
Beryllium
____
____
2p
____
____
2s
____
____
2p
____
[He]2s2p2
____
2s
____
____
2p
____
1s22s2p3
[He]2s2p3
____
2s
____
____
2p
____
1s22s2p4
[He]2s2p4
____
2s
____
____
2p
____
1s22s2p5
[He]2s2p5
____
1s
Neon
____
2s
1s22s2p2
____
1s
Fluorine
____
[He]2s2p1
____
1s
Oxygen
____
2p
1s22s2p1
____
1s
Nitrogen
____
[He]2s2
____
1s
Carbon
____
2s
1s22s2
____
1s
Boron
Noble gas
notation
____
2s
____
____
2p
____
1s22s2p6
[He]2s2p6
____
1s
____
2s
____
____
2p
____
Irregular confirmations of Cr and Cu
Chromium steals a 4s electron to half
fill its 3d sublevel
Copper steals a 4s electron to FILL
its 3d sublevel
Determination of Atomic Radius
Half of the distance between nucli in
covalently bonded diatomic molecule
"covalent atomic radii"
Periodic Trends in Atomic Radius
Radius decreases across a period
Increased effective nuclear charge due
to decreased shielding
Radius increases down a group
Addition of principal quantum levels
Table of
Atomic
Radii
Ionization Energy: the energy required
to remove an electron from an atom
 Increases for successive electrons taken from
the same atom
 Tends to increase across a period
Electrons in the same quantum level do
not shield as effectively as electrons in
inner levels
Irregularities at half filled and filled
sublevels due to extra repulsion of
electrons paired in orbitals, making them
easier to remove
 Tends to decrease down a group
Outer electrons are farther from the
nucleus
Ionization of Magnesium
Mg + 738 kJ  Mg+ + eMg+ + 1451 kJ  Mg2+ + eMg2+ + 7733 kJ  Mg3+ + e-
Table of 1st
Ionization Energies
Electron Affinity - the energy change
associated with the addition of an electron
 Affinity tends to increase across a period
 Affinity tends to decrease as you go down
in a period
Electrons farther from the nucleus
experience less nuclear attraction
Some irregularities due to repulsive
forces in the relatively small p orbitals
Table of Electron Affinities
Electronegativity
A measure of the ability of an atom in a chemical
compound to attract electrons
 Electronegativities tend to increase across
a period
 Electronegativities tend to decrease down a
group or remain the same
Periodic Table of Electronegativities
Ionic Radii
Cations
Anions
Positively charged ions
Smaller than the corresponding
atom
Negatively charged ions
Larger than the corresponding
atom
Table of
Ion Sizes
Summary of Periodic Trends